CN104078586A - Organic light-emitting diode and preparation method thereof - Google Patents
Organic light-emitting diode and preparation method thereof Download PDFInfo
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- CN104078586A CN104078586A CN201310101296.1A CN201310101296A CN104078586A CN 104078586 A CN104078586 A CN 104078586A CN 201310101296 A CN201310101296 A CN 201310101296A CN 104078586 A CN104078586 A CN 104078586A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
The invention provides an organic light-emitting diode which comprises an anode conductive substrate, a light-emitting functional layer, a cathode layer and a packaging layer which are sequentially stacked, wherein the packaging layer comprises first packaging units and second packaging units which are sequentially laminated; the first packaging units sequentially comprise first organic barrier layers, second organic barrier layers and mixed barrier layers; and the second packaging units sequentially comprise third organic barrier layers, fourth organic barrier layers and inorganic barrier layers. The organic light-emitting diode is alternately packaged by multiple material layers, integrates the advantages of an organic material and an inorganic material, is high in compactness, and can effectively reduce corrosion of oxygen and water vapor to the organic light-emitting diode, so that the service life of the organic light-emitting diode is prolonged significantly. The invention further provides a preparation method of the organic light-emitting diode.
Description
Technical field
The present invention relates to organic electroluminescence device, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is between transparent anode and cathode layer, to accompany multilayer organic material film (hole injection layer, hole transmission layer, luminescent layer, electron supplying layer and electron injecting layer), and when applying between electrode after certain voltage, luminescent layer will be luminous.In recent years, organic electroluminescence device because cost of manufacture own is low, the response time is short, luminosity is high, the feature such as wide visual angle, low driving voltage and energy-conserving and environment-protective has been subject to extensive concern in fields such as panchromatic demonstration, backlight and illuminations, and has been considered to be most likely at the device of new generation that occupies dominance on following illumination and display device market.
At present, the problem that organic electroluminescence device average life is shorter, this is mainly because organic material film is very loose, occurs rapidly aging after easily being infiltrated by compositions such as airborne steam and oxygen.In the time of real work, cathode layer 10% work that will have a strong impact on device that is corroded.Therefore, organic electroluminescence device must encapsulate before entering actual use, and the quality of encapsulation is directly connected to the life-span of organic electroluminescence device.
In conventional art, adopt glass cover or crown cap to encapsulate, ultraviolet polymerization resin sealing for its edge, but the glass cover using in this method or crown cap volume are often larger, increased the weight of device, and the method can not be applied to the give out light encapsulation of device of flexible organic electroluminescence.
Thin-film package can effectively intercept water oxygen, reduce thickness of detector and cost.Thin-film package does not re-use metal or glass cover-plate, fluid sealant and drier, can reduce weight and the thickness of device, substitutes mechanical encapsulation part with film moisture separator, also can reduce costs.
Thin-film package is mainly divided into inorganic material encapsulation, organic material encapsulation, organic/inorganic materials encapsulation by material type.The nClear encapsulated layer packaging effect of Beneq Corp. of Finland exploitation is outstanding, but encapsulated layer is inorganic material entirely, in flexible package application, acquires a certain degree of difficulty; Single organic material encapsulation is difficult to effectively intercept water oxygen; The thin-film package excellent organic and inorganic material combines, is adapted at flexible upper application.
For addressing the above problem, at present the plastic substrates that adopt also coordinate the method for multilayer encapsulation to prevent the infiltration of water vapour and oxygen more, but the method can bring luminescent device heat radiation bad and cause the problem reducing device lifetime.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.The inorganic barrier layer of this organic electroluminescence device is chosen the material with thermal conductive resin, and employing multilayer is organic alternately to be encapsulated with inorganic barrier layer, compactness is high, can effectively reduce oxygen and the erosion of steam to organic electroluminescence device, can realize Rapid Thermal conduction and evacuate heat, thus the life-span of improving significantly organic electroluminescence device.The organic electroluminescence device that the inventive method is applicable to prepare with conducting glass substrate, is also applicable to the flexible organic electroluminescent device of preparing as substrate taking plastics or metal.The inventive method is particularly useful for encapsulating flexible organic electroluminescent device.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise the anode conducting substrate, light emitting functional layer, cathode layer and the encapsulated layer that stack gradually, described encapsulated layer comprises the first encapsulation unit and the second encapsulation unit that lamination arranges successively, described the first encapsulation unit comprises successively first organic barrier layer, second organic barrier layer and mixes barrier layer, described the second encapsulation unit comprises the 3rd organic barrier layer, the 4th organic barrier layer and inorganic barrier layer successively
Described mixing barrier layer material is the composite material that metal oxide, metal fluoride and phthalocyanine thing form, and described metal oxide is molybdenum trioxide (MoO
3), vanadic oxide (V
2o
5), tungstic acid (WO
3), cesium oxide (Cs
2o), nickel oxide (NiO) or manganese dioxide (MnO
2), metal fluoride is lithium fluoride (LiF), cerium fluoride (CeF
2), magnesium fluoride (MgF
2), aluminum fluoride (AlF
3), calcirm-fluoride (CaF
2) or barium fluoride (BaF
2), described phthalocyanine thing is CuPc (CuPc), Phthalocyanine Zinc (ZnPc), FePC (FePc), Cobalt Phthalocyanine (CoPc), manganese phthalocyanine (MnPc) or Nickel Phthalocyanine (NiPc),
Described inorganic barrier layer material is the composite material that nitride, metal sulfide and carbide form, and described nitride is silicon nitride (Si
3n
4), aluminium nitride (AlN), boron nitride (BN), hafnium nitride (HfN), tantalum nitride (TaN) or titanium nitride (TiN), described metal sulfide is cadmium sulfide (CdS), vulcanized lead (PbS), ferrous sulfide (FeS
2), copper sulfide (CuS), zinc sulphide (ZnS) or nickel sulfide (NiS), described carbide is carborundum (SiC), tungsten carbide (WC), ramet (TaC), boron carbide (BC), titanium carbide (TiC) or hafnium carbide (HfC);
The material on described first organic barrier layer and the 3rd organic barrier layer is all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq
3), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 1, one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi)
The material on described second organic barrier layer and the 4th organic barrier layer is all selected from 4,7-diphenyl Phen (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), oxine aluminium (Alq
3), two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (Balq) and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, the one in 2,4-triazole (TAZ).
Preferably, in the material on described mixing barrier layer, the shared mass ratio of described metal oxide and phthalocyanine thing is 10～30%; In the material of described inorganic barrier layer, the shared mass ratio of described metal sulfide and carbide is 10～30%.
Preferably, the thickness on described first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer is 200nm～300nm, and the thickness of described mixing barrier layer and inorganic barrier layer is 100nm～200nm.
Preferably, described the first encapsulation unit and the second encapsulation unit alternately repeat to arrange 2～4 times successively.
Anode substrate is conducting glass substrate or conduction organic film substrate.
Preferably, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Cathode layer can be non-transparent metals cathode layer (aluminium, silver, gold etc.), can be also transparent cathode layer (dielectric layer/metal level/dielectric layer structure that dielectric layer tramp metal layer forms etc.).
Preferably, cathode layer is non-transparent metals cathode layer, adopts vacuum deposition method setting.
Described encapsulated layer adopt the first encapsulation unit and the second encapsulation unit successively alternative stacked set-up mode be deposited on cathode layer surface, can protect light emitting functional layer and cathode layer to exempt from destruction in subsequent operation process.Inorganic barrier layer compact structure in described encapsulated layer, can effectively intercept water oxygen and penetrate into device inside, and form metal oxide, metal fluoride, nitride and the selenides of inorganic barrier layer and there is good heat conductivility and water absorbing capacity, can effectively prevent device over-heat inside and cause the situation that the life-span reduces; Its organic barrier layer can make up the fragility shortcoming of inorganic barrier layer effectively, has improved the pliability of device, also can extend water, oxygen permeation pathway, effectively stops the erosion to organic electroluminescence device of extraneous steam and oxygen, thereby extends device lifetime.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
(1) anode pattern that is prepared with organic electroluminescence devices on clean electrically-conductive backing plate forms anode conducting substrate; Adopt the method for vacuum evaporation on anode conducting substrate, to prepare light emitting functional layer and cathode layer;
(2) on cathode layer, prepare encapsulated layer, preparation method is as follows:
(a) making of the first encapsulation unit:
Mode by vacuum evaporation is the organic barrier layer of evaporation first, second organic barrier layer and mix barrier layer successively on described cathode layer surface, and the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
(b) making of the second encapsulation unit:
Adopt the mode of vacuum evaporation evaporation the 3rd organic barrier layer and the 4th organic barrier layer successively on described mixing barrier layer, the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
Method by magnetron sputtering is prepared inorganic barrier layer on described the 4th organic barrier layer, and the base vacuum degree in described magnetron sputtering process is 1 × 10
-5pa～1 × 10
-3pa;
The material on described first organic barrier layer and the 3rd organic barrier layer is all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 2,9-dimethyl-4,7-diphenyl-1, one in 10-phenanthroline and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material on described second organic barrier layer and the 4th organic barrier layer is all selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, one in 2,4-triazole;
The material on described mixing barrier layer is the composite material that metal oxide, metal fluoride and phthalocyanine thing form, described metal oxide is molybdenum trioxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide, described metal fluoride is lithium fluoride, cerium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, and described phthalocyanine thing is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine, Nickel Phthalocyanine; The material of described inorganic barrier layer is the composite material that nitride, metal sulfide and carbide form, described nitride is silicon nitride, aluminium nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, described metal sulfide is cadmium sulfide, vulcanized lead, ferrous sulfide, copper sulfide, zinc sulphide or nickel sulfide, and described carbide is carborundum, tungsten carbide, ramet, boron carbide, titanium carbide or hafnium carbide.
Preferably, in the material on described mixing barrier layer, the shared mass ratio of described metal oxide and phthalocyanine thing is 10～30%; In the material of described inorganic barrier layer, the shared mass ratio of described metal sulfide and carbide is 10～30%.
Preferably, the thickness on described first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer is 200nm～300nm, and the thickness of described mixing barrier layer and inorganic barrier layer is 100nm～200nm.
Preferably, described the first encapsulation unit and the second encapsulation unit alternately repeat to arrange 2～4 times successively.
Anode substrate is conducting glass substrate or conduction organic film substrate.
Preferably, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Preferably, light emitting functional layer is the method setting by vacuum evaporation.
Cathode layer can be non-transparent metals cathode layer (aluminium, silver, gold etc.), can be also transparent cathode layer (dielectric layer/metal level/dielectric layer structure that dielectric layer tramp metal layer forms etc.).
Preferably, cathode layer is non-transparent metals cathode layer, adopts vacuum deposition method setting.
Make described organic electroluminescence device by above-mentioned steps, comprise the anode conducting substrate, light emitting functional layer, cathode layer and the encapsulated layer that are cascading.
Described organic electroluminescence device adopts the alternately encapsulation of multilayer material layer, combines the advantage separately of organic material and inorganic material, and compactness is high, can effectively reduce oxygen and the erosion of steam to organic electroluminescence device, thereby have the higher life-span.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) the first encapsulation unit of organic electroluminescence device of the present invention and the existence of the second encapsulation unit can be protected light emitting functional layer and cathode layer, adopt multilayer material layer to be arranged alternately, compactness is high, can effectively reduce oxygen and the erosion of steam to organic electroluminescence device, and can realize Rapid Thermal conduction and evacuate heat, the life-span of improving significantly organic electroluminescence device;
(2) water resistance of organic electroluminescence device of the present invention (WVTR) reaches 10
-5g/m
2day, the life-span reaches 6,900 hours above (T701000cd/m
2: i.e. initial brightness is 1000cd/m
2, the time that brightness decay to 70% is used);
(3) the inventive method is applicable to the organic electroluminescence device prepared taking electro-conductive glass as anode substrate of encapsulation, is also applicable to the flexible organic electroluminescent device that encapsulation is prepared as anode substrate taking plastics or metal.The inventive method is particularly useful for encapsulating flexible organic electroluminescent device;
(4) organic electroluminescence device material cheapness of the present invention, method for packing technique is simple, and easily large area preparation is suitable for large-scale industrialization and uses.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer, luminescent layer and cathode layer
A. the pre-treatment of conducting glass substrate
Get ito glass substrate, carry out successively acetone cleaning → ethanol cleaning → washed with de-ionized water → ethanol and clean, all clean with supersonic wave cleaning machine, individual event washing is cleaned 5 minutes, then dries up with nitrogen, and stove-drying is stand-by; Ito glass after cleaning is also needed to carry out surface activation process, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface; ITO thickness is 100nm;
B. the preparation of light emitting functional layer, luminescent layer and cathode layer
Adopt the method for vacuum evaporation on ito glass substrate, to form successively hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer; Adopt evaporation to make cathode layer;
The preparation of hole injection layer: evaporation is by the NPB MoO that adulterates on ito glass substrate
3the composite material forming, MoO
3doping mass fraction 30%, this layer thickness is 10nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: evaporation hole transmission layer on hole injection layer, adopt 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) is as hole mobile material, vacuum degree 1 × 10
-5pa, evaporation rate
evaporation thickness 30nm;
The preparation of luminescent layer: evaporation luminescent layer on hole transmission layer, the material of main part of luminescent layer adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), doping mass fraction 5%, vacuum degree 1 × 10
-5pa, evaporation rate
evaporation thickness 20nm;
The preparation of electron transfer layer: evaporation one deck 4 on luminescent layer, 7-diphenyl-1,10-phenanthroline (Bphen) is as electron transport material, vacuum degree 1 × 10
-5pa, evaporation rate
evaporation thickness 10nm;
The preparation of electron injecting layer: evaporation electron injecting layer on electron transfer layer, mixes CsN3 in Bphen doping mass fraction 30%, vacuum degree 1 × 10
-5pa, evaporation rate
evaporation thickness 20nm;
The preparation of cathode layer: evaporation is prepared cathode layer on electron injecting layer, metallic cathode layer adopts aluminium (Al), and thickness is 100nm, vacuum degree 1 × 10
-5pa, evaporation rate
(2) on cathode layer, prepare encapsulated layer
A. the making of the first protected location:
Adopting the mode of vacuum evaporation on cathode layer, to make a layer thickness is that the TPBi film of 200nm is as first organic barrier layer, vacuum degree 1 × 10
-3, evaporation rate
Adopting the mode of vacuum evaporation on first organic barrier layer, to make a layer thickness is that the TAZ film of 220nm is as second organic barrier layer, vacuum degree 1 × 10
-3pa, evaporation rate
Adopt the mode of vacuum coevaporation on second organic barrier layer, to make the mixing barrier layer that a layer thickness is 150nm, described mixing barrier layer is by BaF
2, MnO
2form with tri-kinds of materials of NiPc, shared mass ratio is respectively 67%, 20% and 13%, evaporation rate
vacuum degree 1 × 10
-3;
B. the making of the second protected location:
To make a layer thickness on barrier layer be that the TPBi film of 200nm is as the 3rd organic barrier layer, vacuum degree 1 × 10 to the mode that adopts vacuum evaporation mixing
-3, evaporation rate
Adopting the mode of vacuum evaporation on the 3rd organic barrier layer, to make a layer thickness is that the TAZ film of 220nm is as the 4th organic barrier layer, vacuum degree 1 × 10
-3pa, evaporation rate
Adopt the mode of magnetron sputtering on the 4th organic barrier layer, to make the inorganic barrier layer that a layer thickness is 120nm, taking TiN, NiS and HfC as target, shared mass ratio is respectively 65%, 10% and 25%, vacuum degree 1 × 10
-3pa;
Alternately repeat to prepare the first encapsulation unit and the second encapsulation unit 2 times, form encapsulated layer, obtain organic electroluminescence device.
Water resistance (WVTR, the g/m of the organic electroluminescence device after the present embodiment composite package
2day) be 9.2 × 10
-5, the life-span is 6,870 hours.
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1.As shown in Figure 1, the present embodiment organic electroluminescence device, comprise successively ito glass substrate 1, light emitting functional layer 2, cathode layer 3, encapsulated layer 4, described encapsulated layer is that the lamination combination of the first encapsulation unit 41 and the second encapsulation unit 42 repeats to form for 2 times, wherein, described the first encapsulation unit comprises that the thickness of stack is successively all the TPBi film 411 of 200nm, TAZ film 412 and mixes barrier layer 413, and described the second encapsulation unit comprises that thickness is all the TPBi film 421 of 200nm, TAZ film 422 and inorganic barrier layer 423.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer, luminescent layer and cathode layer
With embodiment mono-;
(2) on cathode layer, prepare encapsulated layer
A. the making of the first protected location:
Adopting the mode of vacuum evaporation on cathode layer, to make a layer thickness is that the NPB film of 300nm is as first organic barrier layer, vacuum degree 1 × 10
-4evaporation rate
Adopting the mode of vacuum evaporation on first organic barrier layer, to make a layer thickness is that the BCP film of 300nm is as second organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of vacuum coevaporation on second organic barrier layer, to make the mixing barrier layer that a layer thickness is 100nm, described mixing barrier layer is by CeF
2, V
2o
5form with tri-kinds of materials of ZnPc, shared mass ratio is respectively 60%, 10% and 30% and is made up of two kinds of materials, evaporation rate
vacuum degree 1 × 10
-5;
B. the making of the second protected location:
To make a layer thickness on barrier layer be that the NPB film of 300nm is as the 3rd organic barrier layer, vacuum degree 1 × 10 to the mode that adopts vacuum evaporation mixing
-4evaporation rate
Adopting the mode of vacuum evaporation on the 3rd organic barrier layer, to make a layer thickness is that the BCP film of 300nm is as the 4th organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of magnetron sputtering on the 4th organic barrier layer, to make the inorganic barrier layer that a layer thickness is 150nm, taking AlN, PbS and WC as target, shared mass ratio is respectively 50%, 20% and 30%, vacuum degree 1 × 10
-4pa;
Alternately repeat to prepare the first encapsulation unit and the second encapsulation unit 3 times, form encapsulated layer, obtain organic electroluminescence device.
Water resistance (WVTR, the g/m of the organic electroluminescence device after the present embodiment composite package
2day) be 8.1 × 10
-5, the life-span is 6,981 hours.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer, luminescent layer and cathode layer
With embodiment mono-;
(2) on cathode layer, prepare encapsulated layer
A. the making of the first protected location:
Adopt the mode of vacuum evaporation on cathode layer, to make the Alq that a layer thickness is 250nm
3film is as first organic barrier layer, vacuum degree 1 × 10
-4evaporation rate
Adopting the mode of vacuum evaporation on first organic barrier layer, to make a layer thickness is that the TPBi film of 250nm is as second organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of vacuum coevaporation on second organic barrier layer, to make the mixing barrier layer that a layer thickness is 160nm, described mixing barrier layer is by MgF
2, WO
3form with tri-kinds of materials of FePc, shared mass ratio is respectively 75%, 20% and 15%, evaporation rate
vacuum degree 5 × 10
-5;
B. the making of the second protected location:
Adopt the mode of vacuum evaporation to make the Alq that a layer thickness is 250nm on mixing barrier layer
3film is as the 3rd organic barrier layer, vacuum degree 1 × 10
-4evaporation rate
Adopting the mode of vacuum evaporation on the 3rd organic barrier layer, to make a layer thickness is that the TPBi film of 250nm is as the 4th organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of magnetron sputtering on the 4th organic barrier layer, to make the inorganic barrier layer that a layer thickness is 140nm, with BN, FeS
2with TaC be target, shared mass ratio is respectively 77%, 10% and 13%, vacuum degree 1 × 10
-4pa;
Alternately repeat to prepare the first encapsulation unit and the second encapsulation unit 3 times, form encapsulated layer, obtain organic electroluminescence device.
Water resistance (WVTR, the g/m of the organic electroluminescence device after the present embodiment composite package
2day) be 8.4 × 10
-5, the life-span is 6,955 hours.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer, luminescent layer and cathode layer
With embodiment mono-;
(2) on cathode layer, prepare encapsulated layer
A. the making of the first protected location:
Adopting the mode of vacuum evaporation on cathode layer, to make a layer thickness is that the m-MTDATA film of 220nm is as first organic barrier layer, vacuum degree 1 × 10
-4evaporation rate
Adopt the mode of vacuum evaporation on first organic barrier layer, to make the Alq that a layer thickness is 240nm
3film is as second organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of vacuum coevaporation on second organic barrier layer, to make the mixing barrier layer that a layer thickness is 150nm, described mixing barrier layer is by AlF
3, Cs
2tri-kinds of materials of O and CoPc form, and shared mass ratio is respectively 60%, 20% and 20%, evaporation rate
vacuum degree 5 × 10
-5;
B. the making of the second protected location:
To make a layer thickness on barrier layer be that the m-MTDATA film of 220nm is as the 3rd organic barrier layer, vacuum degree 1 × 10 to the mode that adopts vacuum evaporation mixing
-4evaporation rate
Adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to make the Alq that a layer thickness is 240nm
3film is as the 4th organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of magnetron sputtering on the 4th organic barrier layer, to make the inorganic barrier layer that a layer thickness is 120nm, taking HfN, CuS and BC as target, shared mass ratio is respectively 70%, 10% and 20%, vacuum degree 1 × 10
-4pa;
Alternately repeat to prepare the first encapsulation unit and the second encapsulation unit 2 times, form encapsulated layer, obtain organic electroluminescence device.
Water resistance (WVTR, the g/m of the organic electroluminescence device after the present embodiment composite package
2day) be 8.5 × 10
-5, the life-span is 6,920 hours.
Embodiment 5
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer, luminescent layer and cathode layer
With embodiment mono-;
(2) on cathode layer, prepare encapsulated layer
A. the making of the first protected location:
Adopting the mode of vacuum evaporation on cathode layer, to make a layer thickness is that the BCP film of 260nm is as first organic barrier layer, vacuum degree 1 × 10
-4evaporation rate
Adopting the mode of vacuum evaporation on first organic barrier layer, to make a layer thickness is that the Balq film of 200nm is as second organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of vacuum coevaporation on second organic barrier layer, to make the mixing barrier layer that a layer thickness is 150nm, described mixing barrier layer is by CaF
2, tri-kinds of materials of NiO and MnPc form, shared mass ratio is respectively 62%, 20% and 18%, evaporation rate
vacuum degree 5 × 10
-5;
B. the making of the second protected location:
To make a layer thickness on barrier layer be that the BCP film of 260nm is as the 3rd organic barrier layer, vacuum degree 1 × 10 to the mode that adopts vacuum evaporation mixing
-4evaporation rate
Adopting the mode of vacuum evaporation on the 3rd organic barrier layer, to make a layer thickness is that the Balq film of 200nm is as the 4th organic barrier layer, vacuum degree 1 × 10
-4pa, evaporation rate
Adopt the mode of magnetron sputtering on the 4th organic barrier layer, to make the inorganic barrier layer that a layer thickness is 100nm, taking TaN, ZnS and TiC as target, shared mass ratio is respectively 70%, 15% and 15%, vacuum degree 1 × 10
-4pa;
Alternately repeat to prepare the first encapsulation unit and the second encapsulation unit 2 times, form encapsulated layer, obtain organic electroluminescence device.
Water resistance (WVTR, the g/m of the organic electroluminescence device after the present embodiment composite package
2day) be 8.9 × 10
-5, the life-span is 6,907 hours.
Embodiment 6
A preparation method for organic electroluminescence device, comprises the following steps:
(1) on anode substrate, prepare light emitting functional layer, luminescent layer and cathode layer
With embodiment mono-;
(2) on cathode layer, prepare encapsulated layer
A. the making of the first protected location:
Adopting the mode of vacuum evaporation on cathode layer, to prepare a layer thickness is that the TAPC film of 200nm is as first organic barrier layer, vacuum degree 1 × 10
-5evaporation rate
Adopting the mode of vacuum evaporation on first organic barrier layer, to make a layer thickness is that the Bphen film of 200nm is as second organic barrier layer, vacuum degree 1 × 10
-5pa, evaporation rate
Adopt the mode of vacuum coevaporation on second organic barrier layer, to make the mixing barrier layer that a layer thickness is 200nm, described mixing barrier layer is by LiF, MoO
3form with tri-kinds of materials of CuPc, shared mass ratio is respectively 60%, 30% and 10%, evaporation rate
vacuum degree 1 × 10
-5;
B. the making of the second protected location:
To make a layer thickness on barrier layer be that the TAPC film of 200nm is as the 3rd organic barrier layer, vacuum degree 1 × 10 to the mode that adopts vacuum evaporation mixing
-5, evaporation rate
Adopting the mode of vacuum evaporation on the 3rd organic barrier layer, to make a layer thickness is that the Bphen film of 200nm is as the 4th organic barrier layer, vacuum degree 1 × 10
-5pa, evaporation rate
Adopt the mode of magnetron sputtering on the 4th organic barrier layer, to make the inorganic barrier layer that a layer thickness is 200nm, with Si
3n
4, CdS and SiC be target, shared mass ratio is respectively 60%, 30% and 10%, base vacuum degree 1 × 10
-5pa;
Alternately repeat to prepare the first encapsulation unit and the second encapsulation unit 4 times, form encapsulated layer, obtain organic electroluminescence device.
Water resistance (WVTR, the g/m of the organic electroluminescence device after the present embodiment composite package
2day) be 7.8 × 10
-5, the life-span is 7,024 hours.
To sum up, the preparation method of organic electroluminescence device provided by the invention can reduce steam and the erosion of oxygen to organic electroluminescence device effectively, the life-span of improving significantly organic electroluminescence device, and can protect cathode layer to exempt from destruction.
Encapsulation rete compactness is most important, can select suitable process conditions according to device detection result.The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, comprise the anode conducting substrate, light emitting functional layer, cathode layer and the encapsulated layer that stack gradually, it is characterized in that, described encapsulated layer comprises the first encapsulation unit and the second encapsulation unit that lamination arranges successively, described the first encapsulation unit comprises successively first organic barrier layer, second organic barrier layer and mixes barrier layer, described the second encapsulation unit comprises the 3rd organic barrier layer, the 4th organic barrier layer and inorganic barrier layer successively
Described mixing barrier layer material is metal oxide, the composite material that metal fluoride and phthalocyanine thing form, described metal oxide is molybdenum trioxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide, described metal fluoride is lithium fluoride, cerium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, described phthalocyanine thing is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine, Nickel Phthalocyanine, described inorganic barrier layer material is nitride, the composite material that metal sulfide and carbide form, described nitride is silicon nitride, aluminium nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, described metal sulfide is cadmium sulfide, vulcanized lead, ferrous sulfide, copper sulfide, zinc sulphide or nickel sulfide, described carbide is carborundum, tungsten carbide, ramet, boron carbide, titanium carbide or hafnium carbide,
The material on described first organic barrier layer and the 3rd organic barrier layer is all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 2,9-dimethyl-4,7-diphenyl-1, one in 10-phenanthroline and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material on described second organic barrier layer and the 4th organic barrier layer is all selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, one in 2,4-triazole.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, in the material on described mixing barrier layer, the shared mass ratio of described metal oxide and phthalocyanine thing is 10～30%; In the material of described inorganic barrier layer, the shared mass ratio of described metal sulfide and carbide is 10～30%.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness on described first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer is 200nm～300nm, and the thickness of described mixing barrier layer and inorganic barrier layer is 100nm～200nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described the first encapsulation unit and the second encapsulation unit alternately repeat to arrange 2～4 times successively.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
(1) anode pattern that is prepared with organic electroluminescence devices on clean electrically-conductive backing plate forms anode conducting substrate; Adopt the method for vacuum evaporation on anode conducting substrate, to prepare light emitting functional layer and cathode layer;
(2) on cathode layer, prepare encapsulated layer, preparation method is as follows:
(a) making of the first encapsulation unit:
Mode by vacuum evaporation is the organic barrier layer of evaporation first, second organic barrier layer and mix barrier layer successively on described cathode layer surface, and the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
(b) making of the second encapsulation unit:
Adopt the mode of vacuum evaporation evaporation the 3rd organic barrier layer and the 4th organic barrier layer successively on described mixing barrier layer, the vacuum degree in described vacuum evaporation process is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
Method by magnetron sputtering is prepared inorganic barrier layer on described the 4th organic barrier layer, and the base vacuum degree in described magnetron sputtering process is 1 × 10
-5pa～1 × 10
-3pa;
The material on described first organic barrier layer and the 3rd organic barrier layer is all selected from 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 2,9-dimethyl-4,7-diphenyl-1, one in 10-phenanthroline and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material on described second organic barrier layer and the 4th organic barrier layer is all selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, one in 2,4-triazole;
The material on described mixing barrier layer is the composite material that metal oxide, metal fluoride and phthalocyanine thing form, described metal oxide is molybdenum trioxide, vanadic oxide, tungstic acid, cesium oxide, nickel oxide or manganese dioxide, described metal fluoride is lithium fluoride, cerium fluoride, magnesium fluoride, aluminum fluoride, calcirm-fluoride or barium fluoride, and described phthalocyanine thing is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, manganese phthalocyanine, Nickel Phthalocyanine; The material of described inorganic barrier layer is the composite material that nitride, metal sulfide and carbide form, described nitride is silicon nitride, aluminium nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, described metal sulfide is cadmium sulfide, vulcanized lead, ferrous sulfide, copper sulfide, zinc sulphide or nickel sulfide, and described carbide is carborundum, tungsten carbide, ramet, boron carbide, titanium carbide or hafnium carbide.
7. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, in the material on described mixing barrier layer, the shared mass ratio of described metal oxide and phthalocyanine thing is 10～30%; In the material of described inorganic barrier layer, the shared mass ratio of described metal sulfide and carbide is 10～30%.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, the thickness on described first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer is 200nm～300nm, and the thickness of described mixing barrier layer and inorganic barrier layer is 100nm～200nm.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described the first encapsulation unit and the second encapsulation unit alternately repeat to arrange 2～4 times successively.
10. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
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Cited By (1)
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| CN105449123A (en) * | 2015-11-18 | 2016-03-30 | 上海大学 | Manufacturing method of water and oxygen barrier layer |
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